Photocatalytic debromination of preloaded decabromodiphenyl ether on the TiO(2) surface in aqueous system

There have been serious concerns about polybromodiphenyl ethers (PBDEs) in the environment because of their global distribution and bioaccumulation. Owing to strong hydrophobicity of PBDEs, the regular photocatalytic system, in which the substrate is solvated in the bulk solution, is not applicable to the removal of the PBDEs in water. In this work, the photocatalytic reduction degradation of decabromodiphenyl ether (BDE209), the most-used PBDEs, was investigated in aqueous system, by pre-adsorbing it on the surface of photocatalyst. It was found that the preloaded BDE209 underwent efficient reductive debromination in aqueous system under irradiation with wavelength larger than 360 nm in the presence of electron donors such as methanol. Our experiments further show that such a preloaded system exhibits different characteristics from that in the organic solution. The meta-debrominated intermediate is predominant in the present system, while the ortho-debrominated one is the main nona-BDE products in the organic solution. In addition, different from other photocatalytic system, the pH has little effect on the photocatalytic reaction. We propose that these differences are originated from the formation of overlayer of hydrophobic BDE209 to limit the motion of BDE209 and the access of water and H⁺/OH⁻ to the TiO₂ surface.     

Congener-specific accumulation and environmental risk assessment of polybrominated diphenyl ethers in diverse Korean sewage sludge types

Industrial, domestic wastewater, and livestock sludge samples were collected from 23 wastewater treatment plants in Korea and analyzed for polybrominated diphenyl ethers (PBDEs). The concentrations of Σ₁₉PBDE ranged from 4.01 to 10,400 ng/g dry weight. The average Σ₁₉PBDE concentrations in industrial, domestic wastewater, and livestock sludge were 1,560?±?3,610, 402?±?148, and 27.6?±?50.4 ng/g dry weight, respectively. The composition of PBDEs differed according to the type of sludge. Among the PBDE congeners, BDE 209 was dominant in all sludge samples. After BDE 209, relatively high levels were found for BDE 28 and 47 from industrial sludge, BDE 47 and 99 from domestic wastewater sludge, and BDE 206, 207, and 208 from livestock sludge. Using hierarchical cluster analysis, sludges were divided into three groups according to PBDE congener composition. A risk assessment of PBDEs in sludge used for soil amendment was carried out. Preliminary results indicated that the potential risk of soil exposed to PBDEs in sludge was relatively low.     

Risk assessment of PBDEs and PAHs in house dust in Kocaeli,Turkey: levels and sources

Indoor dust samples were collected from 40 homes in Kocaeli, Turkey and were analyzed simultaneously for 14 polybrominated diphenyl ethers (PBDEs) and 16 poly aromatic hydrocarbons (PAHs) isomers. The total concentrations of PBDEs (Σ₁₄PBDEs) ranged from 29.32 to 4790 ng g^?1, with a median of 316.1 ng g^?1, while the total indoor dust concentrations of 16 PAHs (Σ₁₆PAHs) extending over three to four orders of magnitude ranged from 85.91 to 40,359 ng g^?1 with a median value of 2489 ng g^?1. Although deca-PBDE products (BDE-209) were the principal source of PBDEs contamination in the homes (median, 138.3 ng g^?1), the correlation in the homes was indicative of similar sources for both the commercial penta and deca-PBDE formulas. The PAHs diagnostic ratios indicated that the main sources of PAHs measured in the indoor samples could be coal/biomass combustion, smoking, and cooking emissions. For children and adults, the contributions to ∑₁₄PBDEs exposure were approximately 93 and 25 % for the ingestion of indoor dust, and 7 and 75 % for dermal contact. Exposure to ∑₁₆PAHs through dermal contact was the dominant route for both children (90.6 %) and adults (99.7 %). For both groups, exposure by way of inhalation of indoor dust contaminated with PBDEs and PAHs was negligible. The hazard index (HI) values for BDE-47, BDE-99, BDE-153, and BDE-209 were lower than the safe limit of 1, and this result suggested that none of the population groups would be likely to experience potential health risk due to exposure to PBDEs from indoor dust in the study area. Considering only ingestion + dermal contact, the carcinogenic risk levels of both B2 PAHs and BDE-209 for adults were 6.2 × 10^?5 in the US EPA safe limit range while those for children were 5.6 × 10^?4 and slightly higher than the US EPA safe limit range (1 × 10^?6 and 1 × 10^?4). Certain precautions should be considered for children.     

Polybrominated diphenyl ethers occurrence in major inflowing rivers of Lake Chaohu (China): Characteristics,potential sources and inputs to lake

Eight commonly occurring polybrominated diphenyl ethers (PBDEs), including BDE 28, 47, 99, 100, 153, 154, 183, 207, and 209, were investigated in water samples from seven major inflowing rivers of Lake Chaohu to determine the distribution characteristics, potential sources and inputs to the lake. The sum of 8 BDE congeners (Σ₈PBDEs) had a concentration varied from 0.31 to 84 ng L⁻¹, with those of BDE 209, BDE 47, BDE 99, and BDE 153 being 0.31–83, <0.012–0.36, <0.012–1.3, and <0.012–0.77 ng L⁻¹, respectively. These levels were in the high range of the global PBDEs concentrations in the water environments. The highest concentrations of Σ₈PBDEs were detected in the western rivers, of which the main pollution sources were strongly related to human activities in urban centers, such as automobile-derived wastes. A sewage treatment plant was likely an important source of the lower brominated BDEs input to one western river. The correlation analyses (all p < 0.05) between PBDEs and DOC, TN, TP, and EC, suggested that the distributions and sources of PBDEs in rivers might also be related with the soil erosion by heave floods. Σ₈PBDEs input to Lake Chaohu from the rivers outlets was estimated at 344 kg yr⁻¹ during the flood season. BDE 209 was the dominant contributor with an input of 340 kg yr⁻¹, followed by BDE 99 (1.3 kg yr⁻¹), BDE 47 (0.83 kg yr⁻¹) and BDE 153 (0.60 kg yr⁻¹).     

Aerobic biotransformation of decabromodiphenyl ether (PBDE-209) by Pseudomonas aeruginosa

Aerobic biodegradation of decabromodiphenyl ether (PBDE-209) by Pseudomonas aeruginosa under the influence of co-metabolic substrates and heavy metal cadmium ion was studied, The results showed that certain amount of co-metabolic substrates, such as glucose, sucrose, lactose, starch, and beef extract, would promote the biodegradation of PBDE-209, among which glucose most favorably accelerated PBDE-209 degradation by about 36% within 5 d. The highest degradation efficiency was reached at the ratio of PBDE-209 and glucose 1:5 while excessive carbon source would actually hamper the degradation efficiency. Exploration of influences of cadmium ion on PBDE-209 biodegradation indicated that degradation efficiency was stimulated at low concentrations of Cd²⁺ (0.5–2 mg L⁻¹) while inhibited at higher levels (5–10 mg L⁻¹), inferring that the heavy metals of different concentrations possessed mixed reactions on PBDE-209 bioremoval. Bromine ion was produced during the biotransformation process and its concentration had a good negative correlation with the residues of PBDE-209. Two nonabromodiphenyl ethers (PBDE-208, PBDE-207), four octabromodiphenyl ethers (PBDE-203, PBDE-202, PBDE-197, PBDE-196) and one heptabromodiphenyl ethers (PBDE-183) were formed with the decomposition of PBDE-209, demonstrating that the main aerobic transformation mechanism of PBDE-209 was debromination.     

Levels, compositions, and inventory of polybrominated diphenyl ethers in sewage sludge of Guangdong Province, South China

Polybrominated diphenyl ethers (PBDEs) were measured in sewage sludge samples collected from major wastewater treatment plants in Guangdong Province, South China. Concentrations of ∑₃₉PBDE (all 39 compounds including tri- to hepta- PBDE congeners except for BDE-209) ranged from 3.6 to 428 ng/g dw with a mean value of 67.4 ng/g dw and a median value of 25.9 ng/g dw, and those of BDE-209 ranged from 9.9 to 5,010 ng/g dw (mean 1,024 ng/g dw and median 824 ng/g dw). The PBDE mixtures detected were mainly comprised of penta-, octa-, and deca-BDEs, with deca-BDE as the dominant constituent. The most abundant congeners, excluding BDE-209, were BDE-47, BDE-99, and BDE-183. Good correlations were found among the concentrations of BDE-47, BDE-99, BDE-100, BDE-138, and BDE-154 (r?>?0.8). However, poor correlations were found between the concentrations of BDE-209 and all other congeners (r?<?0.3). This fact suggests that most tri- to hepta-BDEs detected did not originate from decomposition of deca-BDE. The estimated annual emission of ∑_allPBDEs, ∑₃₉PBDEs, penta-BDE, octa-BDE, and deca-BDE to the Pearl River Delta environment (PRD), based on the sludge samples analyzed, amounts to 232, 20.2, 5.5, 1.7, and 212 kg per year, implicating sewage sludge as a significant source of PBDEs to the PRD environment.     

Contamination and potential sources of polybrominated diphenyl ethers (PBDEs) in water and sediment from the artificial Lake Shihwa, Korea

Concentrations of polybrominated diphenyl ethers (PBDEs) were determined in water and sediment collected from the artificial Lake Shihwa and surrounding creeks. Total concentrations of 23 PBDE congeners in water and sediment ranged from 0.16 to 11.0 ng L⁻¹ and from 1.3 to 18 700 ng g⁻¹ dry weight, respectively. The concentrations of BDE 209 in water and sediment were 1-2 orders of magnitude higher than the total concentrations of other PBDE congeners. The concentrations of total PBDEs and BDE 209 in sediments were the highest compared to previously reported worldwide levels. The highest concentrations of PBDEs in water and sediments were found in creeks near industrial complexes. The PBDE concentrations gradually decreased with increasing distance from the creeks to the inshore and then offshore regions of the lake. BDE 209 was a major congener, accounting for 80% of the total PBDEs in water and sediment, consistent with a high consumption of deca-BDE for the brominated flame retardant market in Korea. Non-parametric multidimensional scaling ordination showed that surrounding creeks are major pathways of PBDE contamination associated with deca-BDE technical mixtures used in industrial complexes around Lake Shihwa. A significant correlation between total organic carbon and total PBDE concentration was found in sediments, and the correlation coefficients for individual PBDE congeners relatively increased from lower to higher brominated congeners.     

Identification and quantification of products formed via photolysis of decabromodiphenyl ether

Background, aim, and scope  Decabromodiphenyl ether (DecaBDE) is used as an additive flame retardant in polymers. It has become a ubiquitous environmental contaminant, particularly abundant in abiotic media, such as sediments, air, and dust, and also present in wildlife and in humans. The main DecaBDE constituent, perbrominated diphenyl ether (BDE-209), is susceptible to transformations as observed in experimental work. This work is aimed at identifying and assessing the relative amounts of products formed after UV irradiation of BDE-209. Materials and methods  BDE-209, dissolved in tetrahydrofuran (THF), methanol, or combinations of methanol/water, was exposed to UV light for 100 or 200 min. Samples were analyzed by gas chromatography/mass spectrometry (electron ionization) for polybrominated diphenyl ethers (PBDEs), dibenzofurans (PBDFs), methoxylated PBDEs, and phenolic PBDE products. Results  The products formed were hexaBDEs to nonaBDEs, monoBDFs to pentaBDFs, and methoxylated tetraBDFs to pentaBDFs. The products found in the fraction containing halogenated phenols were assigned to be pentabromophenol, dihydroxytetrabromobenzene, dihydroxydibromodibenzofuran, dihydroxytribromodibenzofuran, and dihydroxytetrabromodibenzofuran. The PBDEs accounted for approximately 90% of the total amount of substances in each sample and the PBDFs for about 10%. Discussion  BDE-209 is a source of PBDEs primarily present in OctaBDEs but also to some extent in PentaBDEs, both being commercial products now banned within the EU and in several states within the USA. It is notable that OH-PBDFs have not been identified or indicated in any of the photolysis studies performed to date. Formation of OH-PBDFs, however, may occur as pure radical reactions in the atmosphere. Conclusions  Photolysis of decaBDE yields a wide span of products, from nonaBDEs to hydroxylated bromobenzenes. It is evident that irradiation of decaBDE in water and methanol yields OH-PBDFs and MeO-PBDFs, respectively. BDE-202 (2,2′,3,3′,5,5′,6,6′-octabromodiphenyl ether) is identified as a marker of BDE-209 photolysis. Recommendations and perspectives  BDE-209, the main constituent of DecaBDE, is primarily forming debrominated diphenyl ethers with higher persistence which are more bioaccumulative than the starting material when subjected to UV light. Hence, DecaBDE should be considered as a source of these PBDE congeners in the environment. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Assessment of polybrominated diphenyl ethers in eggs of waterbirds from South China

Concentrations of total polybrominated diphenyl ethers (PBDEs) in Ardeid eggs from Hong Kong, Xiamen and Quanzhou in south China ranged from 140-1000, 30-550 and 140-380ngg(-1), lipid wt., respectively. There were spatial and interspecies variations in the abundance and congeneric profiles of PBDEs. The different congeneric profiles observed among the study sites may be associated with the developmental phases of the cities, as well as a possible consequence of debromination of BDE209. Marked concentrations of higher-brominated diphenyl ethers (BDEs 183, 196, 197, 206, 207 and 209) were detected in the egg samples from all sites, probably indicating uptake of BDE209 by top predators, and that there is widespread occurrence of BDE209 in south China. Comparisons of egg concentrations of BDEs 47, 99, 153 and 209 with tentative critical concentrations for neurobehavioral effects and oxidative stress indicated some potential risks for BDE99 and BDE209 in the Ardeid populations.     

Carbonaceous matter and PBDEs on indoor/outdoor glass window surfaces in Guangzhou and Hong Kong,South China

Organic films, collected from indoor and outdoor window surfaces in Guangzhou and Hong Kong of South China, were analyzed to quantify their organic carbon (OC), elemental carbon (EC), and polybrominated diphenyl ethers (PBDEs) content. The highest concentrations of OC, EC, and BDE-209 were found in Guangzhou with values of 10 000 μg m^?2, 2200 μg m^?2, and 4000 ng m^?2, respectively, and the highest concentration of Σ₇PBDE (sum of BDE-28, -47, -99, -100, -153, -154 and -183) was found in Hong Kong with a value of 25 ng m^?2. In most cases, the concentrations of PBDEs were higher in the exterior films than those in the interior films with BDE-209 as the predominant congener in both cities, suggesting that PBDEs mainly come from ambient environment, and deca-BDE accounts for major PBDE consumption. The growth rates of organic film on window surfaces were fast at the beginning, and reached a consistent level afterwards. The evolution rates ranged from 2.6 to 11 nm day^?1 for “bulk film”, while from 0.06 to 0.92 nm day^?1 for “pure film”. The concentrations of PBDEs on the window surfaces did not increase with the growth time, suggesting that the window surface may provide a good place for photo-degradation of PBDEs.     

Occurrence, compositional patterns, and possible sources of polybrominated diphenyl ethers in agricultural soil of Shanghai, China

The present study analyzed surface soil collected from agricultural region of Shanghai to determine the occurrence, compositional patterns and possible sources of polybrominated diphenyl ethers (PBDEs). The results showed that 32 PBDEs were detected among 44 target PBDEs. Total PBDE concentrations ranged from 129 to 1245 ng kg⁻¹ with a mean of 429 ng kg⁻¹. BDE209 was the predominant congener in a range of 33.2-796 ng kg⁻¹ with a mean of 254 ng kg⁻¹. Meanwhile, BDE47, BDE49, BDE153, BDE190, and BDE99 have the most abundant with high concentrations and detectable frequencies. PBDE congeners and homologues analysis and principal component analysis (PCA) also revealed that the major source of PBDE in the soil samples was associated with the prevalent use of technical decabromodiphenyl ether (Deca-BDE) and pentabromodiphenyl ether (Penta-BDE). The correlation analysis proved that there was a significant correlation between total organic carbon (TOC) and lower brominated PBDEs, indicating the significant diffuse nature of the sources of these congeners.     

Levels and distribution of polybrominated diphenyl ethers in plant, shellfish and sediment samples from Laizhou Bay in China

Polybrominated diphenyl ethers (PBDEs) are potentially harmful and persistent environmental pollutants. PBDEs concentrations are reported in plant, shellfish and sediment samples collected from Chinese Laizhou Bay. The summation operator(11)PBDE concentrations in plant and shellfish samples from Laizhou Bay were in the range of 70-5900ngg(-1) and 230-720ngg(-1) lipid, respectively. The summation operator(11)PBDEs concentrations in river sediment intervals samples ranged from 1.3 to 1800ng g(-1) dry weight. Pearson correlation analyses were performed on concentrations of PBDEs congeners of different sediment sample intervals. There were significant positive correlations for BDE 28 and BDE 100 (r=0.945, p<0.01), BDE 47 and BDE 99 (r=0.879, p<0.01), BDE 153 and BDE 154 (r=0.934, p<0.01), nona-BDEs and BDE 209 (r>0.934, p<0.01). BDE 209 was the predominant congener in all analyzed samples, consistent with the fact that deca-BDE technical mixtures are the dominant PBDEs product in Laizhou Bay. Data showed that PBDEs should be considered as an increasing pollution problem in the Laizhou Bay region.     

Levels and distribution of polybrominated diphenyl ethers (PBDEs) in marine fishes from Chinese coastal waters

Concentrations of polybrominated diphenyl ethers (PBDEs) in yellow croakers (Pseudosciaena crocea) and silver pomfrets (Pampus argenteus) collected from nine coastal cities along the eastern China coastline were investigated. PBDE congeners with mono- to hexa-brominated substitutions were detected in the samples, indicating their ubiquitous distribution in the marine environment of China. The total PBDE concentration averaged 3.04 ng g⁻¹ lipid wt, a level that was relatively lower than in other regions of the world, especially North America where Penta-BDE was extensively used. Geographically, the highest concentration of PBDEs was found in Xiamen, and the PBDE levels in yellow croakers were significantly higher than those in pomfrets in most of the selected cities, a pattern which may be related to the different feeding habits of the two species. The congener profiles of PBDEs were found to be different from the commonly detected pattern in fishes from other regions of the world (i.e., BDE47 > BDE99, BDE100 > BDE153, BDE154). BDE47 and BDE154 were the predominant congeners in both species, accounting for more than 60% of the total PBDE concentrations. The reasons for the relatively high proportion of BDE154 may be due to the debromination of higher brominated congeners such as BDE183 and BDE209 by these two species.     

Should apple snail Pomacea canaliculata (Caenogastropoda, Ampullariidae) be used as bioindicator for BDE-209?

Apple snail Pomacea canaliculata has been reported to accumulate polybrominated diphenyl ethers (PBDEs) and was recently proposed as PBDE bioindicator. This work investigates the ability of P. canaliculata to accumulate BDE-209 by dietary exposure under controlled experimental conditions. A 30-day long enrichment feeding assay was carried out using 30 adult apple snails, placed in individual aquaria. Food was enriched at three BDE-209 concentrations (400, 4,700, and 8,300 μg g^?1 lipid weight). Correlation between BDE-209 values in food and snail tissue were estimated according to Stockholm Convention suggested criteria for chemicals with K_OW >5. All animals survived with no evident physical alterations, and all of them accumulated BDE-209. BDE-209 levels in tissue samples increased exponentially with the exposure concentration. The bioaccumulation factor vs. food concentration plot showed a peculiar pattern, in which at intermediate concentrations the snails accumulated less BDE-209 than expected. Our results suggest that P. canaliculata would present a detoxification mechanism for BDE-209 different from the most commonly reported metabolic pathways.     

Polybrominated diphenyl ethers in surface sediments from principal watersheds of Shanghai, China: levels, distribution, influencing factors, and risk assessment

Fourteen and 17 sediment samples were collected from three main rivers of Shanghai in July and November, respectively. Eight polybrominated diphenyl ether (PBDE) congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209) were detected in these samples to clarify the pollution status in the metropolis. Instrumental analyses showed that the concentrations of ∑₈PBDEs ranged from 10.97 to 64.05 ng/g dry weight (dw), with an average value of 29.71 ng/g dw. BDE-209 was the predominant congener accounting for more than 97 % of total PBDEs, followed by BDE-47 and BDE-99. Remarkable spatial and seasonal distributions of PBDE concentrations were observed, suggesting that local sources, seasonal climates, and hydrologic conditions might be the influencing factors. Moderate correlations (r ²?=?0.28–0.51, p?<?0.05) were found between total organic carbon and PBDEs, which indicated that organic carbon content influenced the distributions of PBDEs in sediment of Shanghai at some extent. Hazard quotients revealed PBDEs posed no potential risk to benthic organisms in the study area at present.     

Assessment of polybrominated diphenyl ethers in sediment of Asunle stream of the Obafemi Awolowo University,Ile-Ife,Nigeria

Assessment of levels of polybrominated diphenyl ethers (PBDEs) from the sediment of Asunle stream, an adjourning stream of the Obafemi Awolowo University dumpsite, has been carried out. Sediment samples were collected from the stream at six locations for a period of 8 months, composed of 4 months each of wet (May–Aug) and dry (Nov–Feb) seasons. Soxhlet extraction was employed for the isolation of all the target compounds from the sediment samples. Extracts were further subjected to multi-layer column chromatography employing different forms of silica gel. The prepared samples were analyzed using GC-MS. The overall mean concentrations of the total PBDEs ranged from 1.80 to 9.46 ng/g. The results showed that the concentrations of the PBDEs were slightly higher during the wet season than those during the dry season. In all the studied locations, BDE28, BDE47, BDE99, BDE100, BDE153, and BDE154 were detected in all the sediment samples at concentrations that ranged from 0.73 to 10.43 ng/g. Results of this study indicated that BDE153 was the major pollutant of the Asunle stream sediments.     

Behavior of decabromodiphenyl ether (BDE-209) in soil: effects of rhizosphere and mycorrhizal colonization of ryegrass roots

A rhizobox experiment was conducted to investigate degradation of decabromodiphenyl ether (BDE-209) in the rhizosphere of ryegrass and the influence of root colonization with an arbuscular mycorrhizal (AM) fungus. BDE-209 dissipation in soil varied with its proximity to the roots and was enhanced by AM inoculation. A negative correlation (P < 0.001, R² = 0.66) was found between the residual BDE-209 concentration in soil and soil microbial biomass estimated as the total phospholipid fatty acids, suggesting a contribution of microbial degradation to BDE-209 dissipation. Twelve and twenty-four lower brominated PBDEs were detected in soil and plant samples, respectively, with a higher proportion of di- through hepta-BDE congeners in the plant tissues than in the soils, indicating the occurrence of BDE-209 debromination in the soil-plant system. AM inoculation increased the levels of lower brominated PBDEs in ryegrass. These results provide important information about the behavior of BDE-209 in the soil-plant system.     

Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures

Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2′,4,4′-tetrabromo diphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 °C and 500 °C. The formed reaction products were analysed by high resolution gas chromatography–low resolution mass spectrometry (HRGC-LRMS). Among others brominated–chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated–chlorinated benzenes.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Kinetics and pathways for the debromination of polybrominated diphenyl ethers by bimetallic and nanoscale zerovalent iron: effects of particle properties and catalyst

Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe⁰ slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe⁰ nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe⁰ nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe⁰ are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe⁰ reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role.